Method and apparatus for the refining of viscous hydrocarbon oil



G. R. onn, JR

lqApril 18 1, 1 l i "(METHOD AND APPARATUS FOR TH REFINING OF VISCOUS HYDROCARBON OIL j Filed Aug; 27. 1955. 2 Sheets-Sheet 1 Con ' Enfumncnf Hufcr VII Duo lorfur Chunky Hwhr V Tug-r44 INVENTOR GEORGE RBoun vJR.

Duulvacn' A'ITORNEY AP 1939-. s. R. BOND, JR 2,154,434- 'IIETI l QD AND APPARATUS FOR TIB RBI'IN-ING OI VISCOUS IYDROCARBON OIL v Filed Aug. 27. 19:5 2 Sheets-Sheet 2 ,v IM n ,5 7 "I I I34. l i;

INVENTOR (gone: RBomJ JR A-r'roRNsY i {ff-Pawn is, 1939 d ..bv"PeS$m hem ome w th a solid Q material to remove, und'esirable components therefroml lt has special application to the de- '3 coloriaa'tion ands-purification 101,. petroleum fraca mn i itebl 0 l b cwna'o i t 1 Jt ahasgheehksuggestedin the-.pastthat petroa, l eurn oils of the ilubricatingfrange ma fbe dei p 5 -pplorized byilltrationof the-on through be of manner earth. the. course bf operation,ii lch f bedsybecorne fouled orcontaminat'ed by the idetherein or polymerizedfror adsorbed coloriinpartins and unsteblecr other bodies. To maini tain gor return such to an uncontaminated wcondition, it has been suggested that a liquid be remove deposited material thereiromgbut' always it has; been necessary periodically to remove the Wedge roaster. I Such "regeneration, being necessarilyj uncontrolled or'- very ro hl v controlled,

I gresulted lin' deteriorationof the material as a *dec'olorizins agent, rurther deterioration be1n8 1 occasioned by ,each: such subsequent burning.

' i Such, regenerated'material is lcbmnionly desigated, in refinery terminologm'as onceburned such" material" has been regenerated, the more .xinierior-it is: understooditobaand, after being use'd'iollowing the third orjiourthjegeneratioms,

- ;it is usually, considered not;' to'be worth another,

' j the lubricating'oil range, or similar-materials, it

"may consist of various adsorbent materials which I I I possess the property of removing undesirable com- Qand under such conditions that it will serveas an i reeen rat Y l gIt isan cobject:offthisinvention wembmyian adsorptive or decoloriizln'gn material Y in such trom ,eflecti've decolorizing medium and will becapable mfoifbeing' regeneratedin situ,,i."e., without remov 2' 1118112 110111 the tower or. container in which it I is held" during the, one when oil or other fluid", is being contacted therewith, It is a further'obiect'prthis invention-to provide a system or de- =colorizing and regeneration 'whereby'the' desired I properties or the contact material are not, dele j teriously aflected, at least to any substantialexa I tent,;with each. cycle ,oi operatiomincludinz dex y coloriaationand'regeneration; uoth'er cbjects a d, Quadvantages'will appear, from thedescription as a i --whole.a:i

, terial ,jofl substantially Q uniform void space "fthrouahout', or at leastthroughout each cross' t section thereof, By void spaceis meant the sum mn'rnoolmn ",Arrm'rus ran" THE mt 'Geo'rie B. Bond, Jrl, Paulsboro, N. J., assiznor to Houdry Process Corporation. Dover, Del.,-a cor I I ,porationot-Delaware m gmas-rat 21, m5, sci-lama. 38,02:

- a clum- (cine-141i invention f totthe art eo'i' treatinz I total of v the sp passed through that-bed, at least periodically, to i v filtration material fromits container and'ifree it from deposits whi ch could, not be otherwise 'removed, usually ,by I burning, for example, in a Q ;clay, ftwice'burned clay,- etc., depending 'upon' the number of regenerationsf. The more times t v aces between the individual pieces making up the contact mass. A convenient way to arrive at uniform void space is to employ pieces formly particles may be arrived-at bysuitable methods of grading but alsoby molding the desired gccntactniass into pieces or desired di- "fnie'nsions, for example, suchas described in Patl0 Qentlio. 1,837,97ljissud to Alfred Joseph on Demember-'22, 1931, and in-thecopending'application 'oiEugene J. Houdry, Serial No. 600,581, filed 'March 23, 1932, (Patent No'. 2,078,945;issued May Q1937) and molded particles need not necesll s'arily be of an'nular shape but may consist o! solid particles of cylindrical shape or other refi ifar configurations, tor exampleywhich will pro- 'vide a, contact'mas's having void space 01 about j the "proportion provided where 'cylindrically shaped particles or pastilies are 'employed, or' at leastgenerall'y comparable thereto. Particles of my contacting agent, when in cylindrical form,

may in diameter, or thereabouts. for example, and anysuitable length, e. 8., 2-6 25 Void spacesof the order of 30 to more or less, of the total volumeoi the 'mass or bed of [contact material, and substantially uniform jthroughout each cross section oi the bed of contacting agent, transverse to the direction in which oil or other fluid is passed therethroughfare contemplated.

Where the contacting agent is to be used as a decoiorizing material for petroleum fractions of ponents', such as color bodies, from such oil fractions by polymerization, adsorption, or otherwise. Examples oisuch materials are: argillaceou's hy- ,drosilicatesof alumina, hydrosilicates of alumina as plastic clay, silica gel, or other materials,

whether of a'clayey nature or not, known to have the desired eflects, whicharealso capable of being obtained as particles of suitable dimensions,'or

formed or molded into'particles or pastilles of ,sultable'size andshape;

t I I aterials of such high void space, even though c As my d contacting, agent I employ a mathey have good adsorbent or other necessary icharacteristics ordinarily, or at least often, will which: Fig. 1 shows a flow diagram for a continuous decolorizing process;

Fig. 2 shows a flow diagram for a batch'process oi decolorization; I w

18 Fig. 3 shows suitable apparatus for carrying out such a process, particularly of the continuous type, and for regeneration of the solid decolorlzing material; and

Fig. 4 is a plan view of a section taken through Fig. 3, which shows in detail a unit or member for introducing or withdrawing regeneration -fluld, such as air or gaseous products 'of' combustion, respectively. a I

The drawings will now be analyzed in detail and the treatment of a particular material, viz., petroleum oilof the lubricating range, will be discussed, by way of specific illustration.

' Acontinuous .process is illustrated ,by Fig. '1. w

' stantial decolorization will'occur, must be ascer- Oil is pumped from storage S by pump P through 80 meter M and valve V into-the mixing chamber indicated. Petroleum naphtha, especially light naphtha, e. g. petroleum ether and, which may include propane or butane, is pumped from storage SI by pump Pl through meter Mi and valve VI 85 into the mixing chamber indicated, the pressure maintained being sufliciently high to hold the petroleum ether substantially completely in liquid form, Meters M and MI serve to guide the proportioning of oil to petroleum ether'as desired.

, proportion of propane or petroleum ether which will givethe desired degree of deoolorization with the particular bed of material employed.

shown and from there through either valve V2 or V3 into decolorizer D or DI, respectively, which contains, for example, hydr'osilicate of alumina in the form oi. molded pastilles. One decolorizer 5 is normally out of circuit while the other one is being used. Treated oil leaves decolorizer D or Dithrough valve V4 or V5, respectively, and f passesto the separator shown where petroleum other is separated from treated oil, the former being passed to thecondenser, shown, and from there, by meansof pump P2, reintroduced into petroleum either storage, while the latter is passed to treated oil storage.

-My invention may be illustrated in connection with a batch process of decolorization' by referring to Fig. 2. Oil charge is pumped irom'charging,

tank or. storage S through valve V5 by pump P3 and thence through the heater and valve Vli into the decolorizer, which contains adecolorizto lug bed of material, for, example as above described. During this introduction of oil charge I (usually at atmospheric temperature or above) valves V6, V1 and V8,are closed. Oil is allowed to stand in the decolorizer until it soaks into the pores of the decolorizingbed, i. e, until the bed becomes saturated with absorbed oil, which may take-15 minutes, more or less, for example. Then valve V6 may be opened and the unabsorbed oil.

drained-into temporary storage tank T8, from which it may be intermittently returned to oil Of course, it is, always desired to use the lowest petroleum ether.

storage S by pump Pl. There will be left in the decolorizer a bed of material saturated with oil with no free or unabsorbed oil'in the interstices thereof.

An alternative procedure up to this point is to till the bed of material with charging oil and then to withdraw a part so as to allow oil to stand in the bed to a certain level as, /2 to oi the height of the bed, depending upon the quantity of petroleum ether to be injected, thereby providing for expansion of the latter. The proportions by weight of petroleum ether to oil which have given desirable results in practice are l to 2, 1 toil, ill-to 1,2 to 1, or 3.6 to 1, but other proportions in or near this range may be used.

Now. with valves V6, V1, V9 and VII closed, petroleum ether is passed from storage SI by pump P5 through valve V8 into the decolorizer. The pumping of naphtha, petroleum ether, or the like, into the decolorizer is continued until a pressure is built up sufficient to keep the petroleum) ether substantially in the liquid phase under the temperature and other conditions which obtain.

This may be'require a pressure of 190 or lbs/sq. in., for example. The decolorizer is maintained under such pressure for a period of a few minutesto two or three hours. The minimum amount of time, beyond which no further subtai'ned by trial or experimentation. When this period has elapsed, with valves V6, V1, V8 andstorage S. The exhausted petroleum ether passes through the condenser and is reintroduced into petroleum ether storage Shit necessary by the action of pump P1, v

This operation, i. e., injection of petroleum ,ether and after a period of time exhausting it, [maybe repeated one ormore times if required to reduce the color of the oil to that desired.

From the mixing chamber the mixture of oil and petroleumether ispassed to theheater cient in many cases, particularly where unabsorbed oil is drained from the void spaces of the bed of decolorizing material prior to injection of At the end of the last period during which petroleum etherlis held under pressure in the decolorizer it is not exhausted through valve V9 but, rathen valves V6, V8, V9 and VI 1' are kept closed and valve Vlis opened, allowing petroleum ether and oil to pass therethrough into thesepa rator, from which the-oil passes to the treated oil tank and petroleum ether passes through valve VII) to the condenser and back into petroleum ether storage SI.

By discharging from the bottom of the decolorizer, where petroleum ether is present in liquid form, the major portion of oil can be ejected therefrom. After the initial discharge, the dis-= colorizing bed may be flushed with naphtha or additional quantities ofpetroleum ether to remove more completely the oil from the bed of decolorizing mass.

The regeneration of the bed of deoolorizing material of high void space, which is an importaut consideration" in this invention, can-readily be understood from the apparatus shown in Fig. 3.

A complete cycle'of operation, including a decolorization step followed by a regeneration step, will be described.

i is a casing or chamber, such as shown in v c p M 2,154,434 3 Figuresland 2, containinga clecolorizingmassi ot the mass uniform throughout the horizontal supported therewithin on asuitable screen '3 and w grid I Oil and pet-roleum f"ether are supplied in any suitable proportions, through lines 5 and't 5 respectively, by,controllingvalvesf lic and 5d. The mixture enters thebottoin of chamber l and passes up through the' de'colorizingimass 2T' and ls'emitted inreiined or decolorizedst'ate through s lijneifland valvelai' Another valves areclosed I .1 during the decolorization step. Passage of'oil is- I continued until thematerialj becomes coated or contaminated tosucnan extent that 'oil emerg .hl ou h l ne 7 isnotsufliciently'decolorlzed ortreated, i r I w I I 15 Then the flow of oil petroleum fetherfis c-utgofiandfabsorbe'doil may be washed fromthe' decolorizing mass 2 'byfintroduction o'f'naphtha through conduit 8-"andfvalve 8a and by withfliirawing oil-jnaphtha"jsolution through conduit: 9

. 3 and valve 9a; alltheother valves being closed:

' Now valves {laand 9a areclosedand valves 10a and ila, 'c'ontrolling the leads to interspersed members IO and ;ll respectively; 'are opened. 7 Members!!! andjl l', as shown in Figure, 4, consist I ,or two perforated concentric, annuliland a perfo- .rated straight tube extending inorifa diameter ply linesfJZ andjjl3, are opened] Steam passes j; vvhe i the steam leav ng chamber I; nojlonger carries. appreciable amounts of oil jor naphtha ,with it, all the valves are closed, except valves lOa r or, other oxygen-containing" gas 'i'siintroduced at ontr'olled temperature. through; valve led and through, the, connections shown into perforate, ,yannular members l0, fromwhich it isjiritroduced Where .theftempe'ra'ture of the decolorizingbed ,-happensto ,-bei}below thatatwhichlcombustion "more commonly employed. -must' be below the critical temperature ofthe c e? 1 mmefiedhefiz d col ri i 'p raio is completed, it maybe brought up tolthe desired e m n um r on i n? b e h r-wi e'atedl' to, prevent [the temperature of the mass] from i1exceejding the-. ra nge to which; such may subjected without: substantial depreciation in ts'decolorizing'properties; Byway'of example, here. the decolorizing ,niass consists'fiof molded tame-1a or certainhydrosilicates of-alumina, the a 7 temperature reach during-regeneration shouldnot @xceed 9ooito i2oo F., the lowest temperature at which regeneration will; proceed at a reasonb ri' n d iws eh me rei r bl ai j 'ofcasing or-chamber l are'coveredwith'insula 75 Ytion'lfigvsofas to aid in keepingtheltemperature tep; Thesteamithenpas'ses through'and in 'ohf tact.withidecolorizing mass, 2 and maybe with- .drawn,f'through .v'alve 9a,', 8a'or la,;as1de1sired.-

, When the chanrbera'nd decolorizinglmas'si are I I "up ,td regeneration temperature, the oxygen ,bear- Yingga's is introducedat a temperature suflicientlyj I low to compensate for the exothermioheat of I regeneration, or other-control means such' as an f n fluid-ma be tilizedthereb I independent coon g y u 7 y It ls to be understood that the specific treat- 'ments' described herein bear no limitation upon andvertical cross-sectionsof the chamber. If

, desired,'the casing may be surrounded with a confined annular passageway, through which a water (or low temperature steam) may be circulated during regeneration to withdraw part of the exothermic heat developed, thereby to permit more'rapidregeneration. 1 I

Where a system of decolorization and regenoration, as above illustrated, is employed, a .decolorizing mass may be'used over and over again, 10 only slight, if any,.deterioration resulting from each regeneration. In addition, the mass may be regenerated without removing it from the decolorizing chamber. The high and uniform'porosity of the decolorizing mass and the uniform supply of regenerating medium andwithdrawal of products 'of combustion'are important factors making possibleregeherationof the mass in situ. I a

v While the apparatus of Fig. 3 is discussed in connection with a continuous processof extrac- 80 "tion, by slight modification thereof with regard to'duct's and valves, according to the instruction of theflow diagram of Fig. 2, it is obvious that the same apparatus may be used for batch treatment or decolorization. I a V 85 "Petroleum naphtha or ether, especially light naphtha-and particularly propane and butane, are discussed and particularlycontemplated as v the auxiliary agent capable of 'making a mass U40, and Ilaand valves"IlirandflSaargopened. fAir adapted for regeneration in situ 'function efg flcientlyi as decolorizing material. However, the invention is not limited to such auxiliary agent and any other may be employed, any'type oi auxiliary agentor'itreating or decolorizing operation, where the mass may be regenerated in situ, being contemplated. i

The temperature employed during decolorization'ma'y be, forexample, atmospheric or above.

temperatures as high-949600 F. sometimes being 'employed,although'intermediate temperatures,

for example, atmosphericto 400 F. are the ones The temperature petroleum ether or-other gaseous auxiliary agent, i. e., below the temperature at which such agent will be a permanent gas, under'the pressure con- -'-'ditions"which exist. Superatmospheric pressures this invention, or'upon the. classof fluids which is contemplatedto be treated according to. it. Where in the appended claims thecauxiliary fluidagent, hereinabove illustrated, is described as beingfat least aslow bolling'as naphtha.', it

capabl'e'bf beinglemployed as aids in "decolorozing proces se's, including especially hydrocarbons boil- .ing within the range of propane to heptane-and being directed especially to hydrocarbons boiling 1 prises passing such oil through a' bed of decolorizing material, said bed of materiaibeing made up of an adsorptive blend of silica and alumina molded into piecesor pastilles of regular sizes and shapes to provide large sized void spaces Zip throughout the saidbed of material, said void spaces constituting from 30 to 50% of the total volume of said bed of material, so as to prevent channeling andto permit uniform regeneration in situ or" such bed of material, passing an auxiliary 3g fluid agent capable of effecting removal of undesirable components including color bdies,-comprising a hydrocarbon fluid which is at least as low boiling as naphtha, namely boiling within the range from the boiling point of heptane down to and including that of propane, through said bed of decolorizing material in admixture with the petroleum oil to be decolorized, and at intermittent periods interrupting the passage of oil and auxiliary fluid and regenerating said bed of material in situ to removesolid combustible deposits therefrom. a

2.,In the art of treating a viscous hydrocarbon oil of the lubricating range to remove undesirable components therefrom and to control the color oi the same, the steps of process which comprise passing it in contact with a bed of solid adsorbent,

decolorizing material made up of silicious material molded into pieces or pastilles of regular size and'shape to provide large sized void spaces it to the extent of approximately 30 to 50% of the dill - 'ically unstable bodies, comprising a hydrocarbon total volume of said bed of material and being capable of removing undesirable components from said oil, said contact material being maintained within a confined reaction zone, passing an auxiliary fluid agent capable of removing color-imparting bodies, comprising a hydrocarbon fluid which is'at least as low boiling as naphtha as herein defined, thrcughsaid bed of decolorizing massalong with the petroleum oil to be decolor- 4kg ized, said zone beingmaintained under a sufficiently high pressure so that said auxiliary fluid agent will be maintained predominantly in the liquid phase, and intermittently interrupting the passage of oily and auxiliary fluid into said zone and regenerating said bed of material in situ by passing an oxygen-containing gas therethrough at suitable temperature, and repeating the above steps of process. I p

3. In refining and decolorizing a fluid hydrocarbon oil of the lubricating range, the process which comprises. passing such oil through a bed of solid adsorbent decolorizing material, said bed being made up of silicious material molded into pieces or pastilles of regular sizes and shapes to provide large sized void spaces throughout said bed of material so as to prevent channeling and to permit uniform regeneration in situ, of such bed of material, said voidspaces being of the order of 30 to 50%, of the total volume of said bed of material, passing an auxiliary. fluid agent ca- .pable of effectingremoval of coloredor-chemfluid which is at least as low boiling as naphtha, through said bed of decolorizing material along 0 withthe hydrocarbon oil to be decolorizedi while maintaining the mixture of oil and fluid hydrocarbon agent under sufficient superatmospheric 1 pressure to keep the latter substantially in the liquid phase, the proportion of auxiliary hydroto 4:1; periodically regenerating said bed of contact; material in situ by temporarily interrupting the how of hydrocarbons and passing an oxy gen-containing regenerating fluid therethrough; upon completion orthe. regenerating step, again passingsaidhydrocarbon oil and auxiliary agent through saidbed of solid decolorizing material as above described, and repeating the aforesaid step of process.

4. In refining and decolorizing a fluid petroleum oil of the lubricating range, the process which comprises maintaining a bed of solid decolorizing material within a confined zone. said material being made up of adsorbent silicious material molded into pieces or pastilles of regular sizes and shapes to provide large sized, void spaces throughout the bed of material making up approximately 30 to 50% of the volume of the latter so as to prevent channeling and to permit uniform regeneration in situ of such material, saturating said bed of material with oil to be refined and decolorized, introducing into said confined zone a low-boiling auxiliary fluid agent under sufficient 'superatmospheric" pressure to maintain said agent substantially inliquid phase for precipitating colored or chemically unstable bodies, after a period of time exhausting said fluid agent from said zone by releasing the pressure thereon, again introducing more of said agent under suificient superatmospheric pressure and in liquid phase condition intosaid confined zone in contact with said oil, and finally flushing said oil from the bed of material within said confined zone, the said auxiliary fiuid agent comprising a hydrocarbon fluid which is at least as low boiling as naphtha, and the repeatedinjections of the said auxiliary fluid agent serving to ex- 7 pedite contact of all portions of the oil with the saiddecolorizing material. I

5. Apparatus adapted for decolorizing and treating a viscous hydrocarbon oil to remove undesirable components therefromrwhich com prises acasing providing a reaction chamber, a bed of solid contact material capable, of remov- "ing undesirable constituents from said oil, made up of adsoi'ptive silicious materialmolded into pastilles of regular size and shape-and'providing large sized and substantially uniform void spaces throughout each cross section thereof, located within said chamber, said void's'paces being of the order of 30 to 50% of the total volume. of said bed of contact material, a conduit for-the induction of oil 'communicating'with said chamber adjacent one end thereof and a'conduit for the eduction of oil communicating with said chamber adjacentthe other end thereof, means for continuously introducing a mixture of oil and an auxiliary'fiuid in controlled proportions into said chamber through the said induction conduit,

means comprising a liquid-gas separator joined to said eduction conduit for continuously separating the auxiliary fluid from oil leaving said fchamber, and means including pumps for continuously recycling said auxiliary fluid under sufficient pressure to maintain it predominately in liquid phase," together with 'a stream of fresh -oi1,into said chamber through said induction conduit.

:6. Apparatus adapted for i decoiorizing treating a viscoushydrocarbon oil to remove undesirable components I the:eirom which comprisesa casing providing a. reaction chamber, bed ofsolid contact material capable of remov ing undesirable constituents from said c-il, made up of hydrosilicate of alumina molded into par.

tiiles of regular sizes and shapes soas to provide large sized'void spaces which are substantially a,1sa,asa 8 uniform throughout each cross section oi said bed oi material. located within said chamber,

" said void spaces making up from 30 to 50% of the total volume of said bed of contact material, valved conduits tor the induction or oil into and f its eduction from said chamber connected to the latter, a valvedconduit oommunicatin: with said chamber and with means for introducing a normally gaseous auxiliary hydrocarbon iluid therethrough into said chamber under suiiicient superatmospheric pressure to maintain it in liquid phase, and means adapted and located so as periodically to exhaust auxiliary fluid as a as from said chamber without exhausting the oil therefrom.

015086! R. BOND. JR. 

